Multi-dimensional steric effect for XeI* (B) formation in the oriented Xe* (3P2, MJ = 2) + oriented CH3I reaction

Abstract

Multi-dimensional steric effect for the XeI* (B) formation in the oriented Xe* ((3)P(2), M(J) = 2) + oriented CH(3)I reaction has been observed as a function of the mutual configuration between the molecular orientation and the atomic alignment in the collision frame. The molecular steric opacity function has been determined as a function of the atomic orbital alignment. The large molecular orientation dependence (i.e., the largest reactivity at the I-end and the large difference in the reaction probability between the I-end and the CH(3)-end) and the large molecular alignment dependence (the poor reactivity at the sideway) is recognized for each atomic orbital alignment. In addition, a clear correlation between the molecular orientation and the atomic orbital alignment is recognized (i.e., the L(Z)' = 0 atomic orbital alignment is favorable for the molecular axis direction, while the |L(Z)'| = 1 atomic orbital alignment is favorable for the sideway direction).

Stereo correlated dynamics in the energy transfer process of aligned N2 (A 3Σu+) + oriented NO (X 2Π, Ω = 1/2) → NO (A 2Σ+) + N2 (X 1Σg+)

“…[37][38][39][40] The apparatus is composed of two stateselectors. One is a 500-mm long electrostatic hexapole for the oriented NO (X 2 ) molecular beam, which is constructed with the 500-mm long cylindrical stainless steel rods (r 0 = 4 mm in diameter) mounted with r 0 = 0.565R 0 (R 0 is the distance between the inside surfaces of rods on opposite sides of the hexapole).…”

“…Although the multidimensional aspect of the steric effect on reactive collision is one of the important subjects in the stereodynamics, the direct experimental study is extremely limited even for the atom-molecule reactions. [37][38][39][40] The reaction of N 2 (A 3 u + ) with diatomic molecules should become one of the paradigms for the open-shell molecule-molecule reaction systems as a prototypical four-atom reaction. For the first time, we have succeeded in studying the multidimensional steric effect on the molecular-molecular reaction.…”

Multidimensional steric effect for the XeF* (B, C) formation in the oriented Xe* (3P2, MJ= 2) + oriented NF3reaction

“…A variety of molecular beam experiments has provided direct observation of steric requirements in chemical reactions. So far, the steric effect on the reactive collision has been studied by using the electrostatic hexapole method, [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17] the brute force method, [18][19][20] and the optical pumping method. [21][22][23] In general, the steric effect in the reaction dynamics should essentially be seen from a multidimensional perspective because the reaction dynamics between two reactants having anisotropic structure should depend on the mutual orientation between two reactants.…”

“…The direct experimental studies on the multidimensional steric effects on reactive collision are extremely limited. [13][14][15][16][17] The formation of electronically excited rare-gas halide RgX * from the reactions of metastable rare-gas Rg* ( 3 P 2 ) with polyatomic halogen containing molecules RX is important as a benchmark system to study the multidimensional steric effects on reactive collisions because Rg* ( 3 P 2 ) has an anisotropic electronic structure, (n À 1)p 5 ns 1 . The non-closed shell of Rg + gives rise to two different excited rare gas halide product states, RgX* (B, O = 1/2) and RgX* (C, O = 3/2), that correlate with Rg + ( 2 P 3/2 ) and X À ( 1 S 0 ).…”

“…Most recently, we have studied the multidimensional steric effects for the excimer (XeX*) formations in the reactions of the oriented Xe* ( 3 P 2 , M J = 2) with the oriented molecules having a molecular geometry like CY 3 X (e.g., CF 3 I, CH 3 I, CF 3 Br) [14][15][16] and CX 3 Y (e.g., CCl 3 F) 17 which commonly have relatively large quenching cross sections (s Q B a few hundred A ˚2). [24][25][26][27][28][29] Although the X(or X 3 )-end is commonly most reactive as expected from the chemical intuition like ''steric hindrance'' due to the non-reactive bulky group CY 3 (or Y), every system exhibits a wide range of molecular orientation (and alignment) dependence affected by the atomic orbital alignment which does not correlate well with the chemical intuition.…”